**4. Conclusion**

56 Recent Advances in Crystallography

field, up to 10 T.

17 T and high pressure up to 5 GPa at 1.5 K.

from the timing modes and a fast readout (0.1 s) Frelon CCD based camera. An other upgrade example concerns the ID20 magnetic scattering beamline with an extend of its experimental conditions in order to provide new research opportunities. It is also planned to build a dedicated station for very low temperatures below 1 K, high magnetic fields up to

The world's leading spallation neutron source, ISIS, has contributed significantly to many of the major breakthroughs in materials science, physics and chemistry since it was commissioned in 1985. To keep the UK at the forefront of neutron research, it was decided in 2003 to build a second spallation neutron source, ISIS Target Station 2, where three key areas of science are planned to be investigated in priority: soft matter, bio-sciences and advanced materials. ISIS TS-2 project was completed in 2009 on time and to budget. There are currently 7 available instruments (and 4 instruments under building) at ISIS TS-2 which has a capacity for a total of 18 instruments in the future, adding to the 20 instruments already available at ISIS Target Station 1. Concerning the new instruments dedicated to extreme condition measurements, the available WISH instrument (Chapon et al., 2011) is a long-wavelength diffractometer primarily designed for powder diffraction at long d-spacing in magnetic and large unit cell systems, with the option of enabling single-crystal and polarised beam experiments. The WISH sample environments include a dedicated low background cryostat (with ultra-low temperature inserts), a dedicated 13.6 T vertical magnet, but also the standard ISIS furnaces, pressure cells and gas rigs. Futhermore, there is the IMAT instrument (Kockelmann et al., 2007), in design phase and operating in 2015, which will be a neutron imaging and diffraction instrument for materials science, materials processing and engineering. IMAT will offer a unique combination of imaging and spatially resolved diffraction modes for *tomography-driven diffraction*: residual stresses inside engineering-sized samples can be more effectively analysed if the diffraction scans are guided by radiographic data. Finally, the future EXEED instrument (McMillan and Tucker, 2007) will be a neutron time-of-flight diffractometer optimised for extreme environment studies of materials which will complement the capabilities of WISH on Target Station 2 and PEARL on Target Station 1. The experiments will be performed at high pressure, above 50 GPa using diamond anvil cells, under combined very low temperatures (mK), very high temperatures (2000 K, including laser heating in cells) or intense magnetic

Finally, the neutron reactor installations and instruments at the ILL are undergoing a modernisation phase called the *Millennium programme 2001-2014*, 30 years after the first experiments in 1972. During the first phase (2001-2008) of the ILL upgrade, significant advances had been provided. The efficiency of the instruments has been boosted by a factor of 19. Moreover, 6 new instruments were built and 8 others were upgraded. In the second phase (2008-2014), 7 new instruments are planned to be built and 4 actual instruments upgraded. For extreme conditions experiments, it was planned a new neutron diffractometer XtremeD (Rodriguez-Velamazan et al., 2011). This instrument will be optimized for high pressure, up to 30 GPa, and high magnetic field, up to 15 T in continuous mode, studies for both single crystals and powders. The diffractometer, Since the first crystallographic experiment at the beginning of the 20th century, scientists have always whished to push back frontiers of measurements. Obtaining the structureproperties relationships in static and dynamic modes is one fundamental goal to increase our knowledge of materials and verify existing theories. This was largely made possible by the arrival of modern Large scale facilities allowing material investigations under extreme conditions. State-of-the-art crystallographic measurements discussed in this review and recent upgrades achieved at most facilities augur that limits will be increasingly crossed in the next years, giving rise to unsuspected highlight researches in all domains of sciences. The considered perspectives will offer new opportunities in crystallography.

#### **Author details**

Legrand Vincent *LUNAM Université - Université de Nantes - Ecole Centrale Nantes, Institut de Recherche en Génie Civil et Mécanique (GeM), France vincent.legrand@univ-nantes.fr* 

#### **5. References**


Bull, C. L., Guthrie, M., Archer, J., Fernandez-Diaz, M-T., Loveday, J. S., Komatsu, K., Hamidov, H. & Nelmes, R. J. (2011). High-pressure single-crystal neutron diffraction to 10 GPa by angle-dispersive techniques. *J. Appl. Cryst.*, Vol.44, pp.831-838

58 Recent Advances in Crystallography

pp. 282

pp. 952-953

*Nature*, Vol.135, pp. 342

*ILL Tech. Report* 77/74

apparatus. *Rev. Sci. Instrum.*, Vol.35, pp.175-182

personal view. *Acta Cryst. A*, Vol.64, pp.218-231

Bragg, W. H. (1912). X-rays and crystals. *Nature*, Vol.90, pp. 219 Bragg, W. H. (1913a). X-rays and crystals. *Nature*, Vol.90, pp. 572

Bragg, W. L. (1920). Crystals structure. *Nature*, Vol.105, pp. 646-648

surfactants. *Angewandte Chemie Int. Ed.*, Vol. 51, pp.2414-2416

*Research : an International Journal*, Vol.29, pp.306-316

*Condens. Matter*, Vol.14, pp.1957-1966

*Rev. Sci. Instrum.*, Vol.72, pp.1270-1272

Barcza, A., Gercsi, Z., Knight, K. S. & Sandeman, K. G. (2010). Giant Magnetoelastic Coupling in a metallic helical metamagnet. *Phys. Rev. Letters*, Vol.104, pp.247202 Barnet, J. D. & Hall, H. T. (1964). High pressure – high temperature, X-ray diffraction

Bassett, W. A., Takahashi, T. & Stook, P. W. (1967). X-ray diffraction and optical observations on crystalline solids up to 300 kbar. *Rev. Sci. Instrum.*, Vol.38, pp.37-42 Bassett, W. A. (2001). The birth and development of laser heating in diamond anvil cells.

Basu, A., Chandra, A. Tyagi, A. K. & Mukherjee, G. D. (2012). Reppearance of ferroelectric soft modes in the paraelectric phase of Pb1-xCaxTiO3 at high pressures : Raman and X-

Beson, J. M., Nelmes, R. J., Hamel, G., Loveday, J. S., Weill, G. & Hull, S. (1992). Neutron

Bilderback, D. H., Elleaume, P. & Weckert, E. (2005). Review of third and next generation synchrotron light sources. *J. Phys. B: At. Mol. Opt. Phys.*, Vol.38, pp.S773-S797 Boldyreva, E. V. (2008). High-pressure diffraction studies of molecular organic solids. A

Born, M. (1933). Modified field equations with a finite radius of the electron. *Nature*, Vol.132,

Born, M. (1935). Quantised field theory and the mass of the proton. *Nature*, Vol.136,

Born, M. & Schrödinger, E. (1935). The absolute field constant in the new field theory.

Bousseksou, A., Molnar, G., Salmon, L. & Nicolazzi, W. (2011). Molecular spin crossover phenomenon:recent achievements and pospects.*Chem. Soc. Rev.*, Vol.40, pp.3313-3335

Brochier, D. (1977). Cryostat à température variable pour mesures neutroniques ou optiques.

Bromiley, G. D., Redfern, S. A. T., Le Godec, Y., Hamel, G. & Klotz, S. (2009). A portable high-pressure stress cell based on the V7 Paris-Edinburgh apparatus. *High pressure* 

Brown, P. J., Forsyth, J. B., Lelièvre-Berna, E. & Tasset, F. (2002). Determination of the magnetization distribution in Cr2O3 using spherical neutron polarimetry. *J. Phys.:* 

Brown, P., Bushmelev, A., Butts, C. P., Cheng, J., Eastoe, J., Grillo, I., Heenan, R. K. & Schmidt, A. M. (2012). Magnetic control over liquid surface properties with responsive

Bragg, W. H. (1913b). The reflection of X-rays by crystals. *Nature*, Vol.91, pp. 477 Bragg, W. H. (1915a). The distribution of the electrons in atoms. *Nature*, Vol.95, pp. 344 Bragg, W. H. (1915b). The structure of magnetite and the spinels. *Nature*, Vol.95, pp. 561 Bragg, W. H. & Bragg, W. L. (1913). The structure of diamond. *Nature*, Vol.91, pp. 557

ray diffraction studies. *J. Phys.: Condens. Matter*, Vol.24, pp.115404

powder diffraction above 10 GPa. *Physica B*, Vol.180-181, p.907-910

	- *http://www.esrf.eu/AboutUs/Upgrade/documentation/purple-book/*, Vol.1-2

60 Recent Advances in Crystallography

pp. 640-642

Vol.40, pp.526-531

Vol.135, pp.217-235

*Matter*, Vol.16, pp.1211-1230

*Nature*, Vol.483, pp.576-579

pp.751

Synchrotron. *J. Appl. Phys.*, Vol.18, pp. 810-818 ESRF (2007). Science and technology programme 2008-2017.

Elder, F. R.; Gurewitsch, A. M.; Langmuir, R. V. & Pollock, H. C. (1947). A 70 MeV

Falconi, S., Lundegaard, L. F., Hejny, C. & McMahon, M. I. (2005). X-ray diffraction study of

Fermi, E. (1934). Radioactivity induced by neutron bombardment. *Nature*, Vol.133, pp. 757 Fermi, E. (1940). Reactions produced by neutrons in heavy elements. *Nature*, Vol.146,

Fermi, E. (1947). Elementary theory of the chain-reacting pile. *Science*, Vol.105, pp. 27-32 Fertey, P., Argoud, R., Bordet, P., Reymann, J., Palin, C., Bouchard, C., Bruyère, R., Wenger, E. & Lecomte, C. (2007). A mini-goniometer for X-ray diffraction studies down to 4 K on four-circle diffrctometers equipped with two-dimensional detectors. *J. Appl. Cryst.*,

Fiquet, G. & Andrault, D. (1999). Powder X-ray diffraction under extreme conditions of

Formitchev, D. V., Novozhilova, I. & Coppens P. (2000). Photo-induced linkage isomerism of transition metal nitrosyl and dinitrogen complexes studied by photocrystallographic

Garcia, P., Dahaoui, S., Fertey, P., Wenger, E. & Lecomte, C. (2005). Crystallographic investigation of temperature-induced phase transition of the tetrathiafulvalene-*p*-

Garcia, P., Dahaoui, S., Katan, C., Souhassou, M. & Lecomte, C. (2007). On the accuracy of intermolecular interactions and charge transfer: the case of TTF-CA. *Faraday Discussions*,

Gembicky, M. & Coppens, P. (2007). On the desing of ultrafast shutters for time-resolved

Givord, F., Boucherle, J-X., Lelièvre-Berna, E. & Lejay, P. (2004). The cerium magnetic form facto rand diffuse polarization in CeRh3B2 as functions of temperature. *J. Phys.: Condens.* 

Godfrin, H., Meschke, M., Lauter, H-J., Sultan, A., Böhm, H. M., Krotscheck, E. & Panholzer, M. (2012). Observation of a roton collective mode in a two-dimensional fermi liquid.

Goedhart, J., Stetten, D., Noirclerc-Savoye, M., Lelimousin, M., Joosen, L., Hink, M. A., Weeren, L., Gadella Jr, T. W. J. & Royant, A. (2012). Structure-guided evolution of cyan fluorescent proteins towards a quantum yield of 93%. *Nature Communications*, Vol.3,

Goujon, A., Gillon, B., Gukasov, A., Jeftic, J., Nau, Q., Codjovi, E. & Varret, F. (2003). Photoinduced molecular switching studied by polarized neutron diffraction. *Physical* 

bromanil, TTF-BA charge transfer complex. *Phys. Rev B*, Vol.72, pp.104115

synchrotron experiments*. J. Synchrotron Rad.*, Vol.14, pp.133-137

*Review B*, Vol.67, pp.220401(R). DOI: 10.1103/PhysRevB.67.220401

http://prb.aps.org/abstract/PRB/v67/i22/e220401

*http://www.esrf.eu/AboutUs/Upgrade/documentation/purple-book/*, Vol.1-2

liquid Cs up to 9.8 GPa. *Phys. Rev. Letters*, Vol.94, pp.125507 Fermi, E. (1930). Magnetic moment of atomic Nuclei. *Nature*, Vol.125, pp. 16

pressure and temperature. *J. Synchrotron Rad.*, Vol.6, pp.81-86

techniques. *Tetrahedron*, Vol.56, pp.6813-6820


http://iopscience.iop.org/0953-8984/16/14/025

apparatus for neutron diffraction investigations on high temperature liquids. *Rev. Scientific Instruments*, Vol.77, pp.053903


Legrand, V., Le Gac, F., Guionneau, P. & Létard., J-F. (2008). Neutron powder diffraction studies of two spin transition Fe(II)-complexes under pressure. *Journal of Applied Crystallography*, Vol.41, pp.637-640

62 Recent Advances in Crystallography

Vol.353, pp.1705-1712

pp.10479-10481

pp.1016-1019

*Scientific Instruments*, Vol.77, pp.053903

apparatus for neutron diffraction investigations on high temperature liquids. *Rev.* 

Hennet, L., Pozdnyakova, I., Cristiglio, V., Krisnan, S., Bytchkov, A., Albergamo, F., Cuello, G. J., Brun, J-F., Fischer, H. E., Zanghi, D., Brassamin, S., Saboungi, M-L. & Price, D. L. (2007). Structure and dynamics of levitated liquid aluminates. *J. Non-Crystalline Solids*,

Hennet, L., Pozdnyakova, I., Bytchkov, A., Cristiglio, V., Zanghi, D., Brassamin, S., Brun, J-F., Leydier, M. & Price, D. L. (2008). Fast X-ray scattering measurements on high

Hu, J., Xu, J., Somayazulu, M., Guo, Q., Hemley, R. & Mao, H. K. (2002). X-ray diffraction and laser heating: application of a moissanite anvil cell. *J. Phys.: Condens. Matter*, Vol.14,

Jamieson, J. C., Lawson, A. W. & Nachtrieb, N. D. (1959). New device for obtaining X-ray diffraction patterns from substances exposed to high pressure. *Rev. Sci. Instrum*., Vol.30,

Katsumata, K. (2005). Synchrotron X-ray diffraction studies of magnetic materials under

Kockelmann, W., Oliver, E. C. & Radaelli, P. G. (2007). IMAT - an imaging and materials science & engineering facility for TS-II. Draft proposal for discussion.

Kuhs, W. F., Archer, J. & Doran, D. (1993). A closed-shell furnace for neutron single-crystal

Le Godec, Y., Dove, M. T., Redfern, S. A. T., Tucker, M. G., Marshall, W. G., Syfosse, G. & Klotz, S. (2003). Recent developments using the Paris-Edinburgh cell for neutron diffraction at high pressure and high temperature and some applications. *High Pressure* 

Legrand, V. (2005). Cristallographie et photo-cristallographie haute résolution de composés moléculaires à transition de spin : propriétés structurales, électroniques et mécanismes

Legrand, V., Carbonera, C., Pillet, S., Souhassou, M., Létard, J-F., Guionneau, P. & Lecomte C. (2005). Photo-crystallography: from the structure towards the electron density of

Legrand, V., Pillet, S., Souhassou, M., Lugan, N. & Lecomte C. (2006). Extension of the experimental electron density analysis to metastable states : a case example of the spin

Legrand, V., Pillet, S., Carbonera, C., Souhassou, M., Létard, J-F., Guionneau, P. & Lecomte C. (2007b). Optical, magnetic and structural properties of the spin crossover complex [Fe(btr)2(NCS)2].H2O in the light-induced and thermally quenched metastable states.

crossover complex Fe(btr)2(NCS)2.H2O. *J. Am. Chem. Soc.*, Vol.126, pp.13921 13931 Legrand, V., Pillet, S., Weber, H-P., Souhassou, M., Létard, J-F., Guionneau, P. & Lecomte C. (2007a). On the precision and accuracy of structural analysis of light-induced metastable

de conversion. *thesis, Univ. Henri Poincaré, Nancy 1 (France)*, n°1132

metastable states. *Journal of Physics: Conf. Series*, Vol.21, pp.73-80

temperature levitated liquids. *J. Non-Crystalline Solids*, Vol.354, pp.5104-5017

Katrusiak, A. (2008). High-pressure crystallography. *Acta Cryst. A*, Vol.64, pp.135-148

extreme conditions. *Physica Scripta*, Vol.71, pp.CC7-13

*http://www.isis.stfc.ac.uk/Instruments/Imat/*

*Research*, Vol.23, pp.281-287

diffraction. *J. Appl. Cryst.*, Vol.26, pp.730-733

states. *J. Appl. Cryst.*, Vol.40, pp.1076-1088

*European Journal of Inorganic Chemistry*, pp.5693-5706


Mori, T., Ichiyanagi, K., Sawa, H. & Koshihara, S. (2007). Developing 100 ps-resolved Xray structural analysis capabilities on beamline NW14A at the Photon Factory Advanced Ring. *J. Synchrotron Rad.*, Vol.14, pp.313-319


Seta, J., Ma, J., Davis, S. A., Meldrum, F., Gourrier, A., Kim, Y-Y., Schilde, U., Sztucki, M., Burghammer, M., Maltsev, S., Jäger, C. & Cölfen H. (2012). Structure-preoperty relationships of a biological mesocrystal in the adult sea urchin spine. *PNAS*, Vol.109, pp.3699-3704

SPring-8 (2012). SPring-8 upgrade plan preliminary report. *http://www.spring8.or.jp/en/about\_us/whats\_sp8/spring-8\_II/*.

64 Recent Advances in Crystallography

Mori, T., Ichiyanagi, K., Sawa, H. & Koshihara, S. (2007). Developing 100 ps-resolved Xray structural analysis capabilities on beamline NW14A at the Photon Factory

Ohtani, A., Mizukami, M., Katayama, M., Onodera, A. & Kawai, N. (1977). Multi-anvil apparatus for high pressure X-ray diffraction. *Jpn. J. Appl. Phys.*, Vol.16, pp.1843-1848 Okada, J. T., Sit, P. H-L., Watanabe, Y., Wang, Y. J., Barbiellini, B., Ishikawa, T., Itou, M., Sakurai, Y., Bansil, A., Ishikawa, R., Hamaishi, M., Masaki, T., Paradis, P-F., Kimura, K., Ishikawa, T., & Nanao S. (2012). Persistence of covalent bonding in liquid silicon probed

Orosel, D., Dinnebier, R. E., Blatov, V. A. & Jansen, M. (2012). Structure of a new highpressure – high temperature modification of antimony(III)oxyde, γ-Sb2O3, from high-

Paolasini, L., Detlefs, C., Mazzoli, C., Wilkin, S., Deen, P. P., Bombardi, A., Kernavanois, N., de Bergevin, F., Yakhou, F., Valade, J. P., Brslavetz, I., Fondacaro, A., Pepellin, G. & Bernard, P. (2007). ID20: a beamline for magnetic and resonant X-ray scattering

Paureau, J. (1975). Nouveau dispositif d'étanchéité pour hautes pressions. *Revue de Physique* 

Pillet, S., Legrand, V., Weber, H-P., Souhassou, M., Létard, J-F., Guionneau, P. & Lecomte C. (2008). Out-of-equilibrium charge density distribution of spin crossover complexes from steady-state photocrystallographic measurements : experimental methodology and

Price, T. C., Grant, D. M., Legrand, V. & Walker G. S. (2010). Enhanced kinetics for the LiBH4:MgH2 multi-component hydrogen storage system - the effects of stoichiometry and decomposition environment on cycling behavior. *International Journal of Hydrogen* 

Riekel, C., Müller, M. & Vollrath, F. (1999). In situ X-ray diffraction during forced silking of

Riekel, C. & Vollrath, F. (2001). Spider silk fibre extrusion: combined wide- and small-angle X-ray microdiffraction experiments. *Inter. J. Biological Macromol.*, Vol.29, pp.203-210 Rodriguez-Velamazan, J. A., Campo, J., Rodriguez-Carvajal, J. & Noguera, P. (2011). XtremeD - a new neutron diffractometer for high pressures and magnetic fields at ILL

Sakai, I., Murai, K., Jiang, L., Umesaki, N., Honma, T. & Kitano, A. (2005). Aerodynamic levitation apparatus for structure study of high temperature materials coupled with Debye-Scherrer Camera at BL19B2 of Spring-8. *J. Electron Spectroscopy and Related* 

Scanlon, D. O., Kehoe, A. B., Watson, G. W., Jones, M. O., David, W. I. F., Payne, D. J., Egdell, R. G. Edwards, P. P. & Walsh, A. (2011). Nature of the band gap and origin of the conductivity of PbO2 revealed by theory and experiment. *Phys. Rev. Letters*, Vol.107,

resolution synchrotron powder diffraction data. *Acta Cryst. B*, Vol.68, pp.1-7

investigations under extreme conditions. *J. Synchrotron Rad.*, Vol.14, pp.301-312 Paszkowicz, W. (2002). High pressure powder X-ray diffraction at the turn of the century.

Advanced Ring. *J. Synchrotron Rad.*, Vol.14, pp.313-319

by inelastic x-ray scattering. *Phys. Rev. Lett.*, Vol.108, pp.067402

*Nucl. Instr. And Meth. In Phys. Res. B*, Vol.198, pp.142-182

*Appliquée*, Vol.10, pp.475-478

*Energy*, Vol.35(9), pp.4154-4161

*Phenomena*, Vol.114-147, pp.1011-1013

pp.246402

results. *Z. Kristallogr.*, Vol.223, pp.235-249

spider silk. *Macromolecules*, Vol.32, pp.4464-4466

developed by Spain*. J. Phys.: Conference Series*, Vol.325, pp.012010

